Vat dyestuffs and process of making same



Patented Mar. 19, x

- UNITED STATES PATENT, OFFICE.

GEORG KALISCHER, OF lFRANKFORT-ON-THE-MAIN, AND WERNER ZERWEGK, OF FECHENHEIM', NEAR FRANKFORT-ON-THE-MAIN, GERMANY, ASSIGNORS TO GRAS- SELLI DYESTU'FF CORPORATION, OF NEW YORK, N. Y., A CORPORATION OF DELA- VA'I DYESTUFFS AND PROCESS OF MAKING SAME. No Drawing. Application filed July 8, 1926, Serial No. 121,283, and in Germany July 20, 1925. V We have found that new and very valuable tions the 1.1-dinaphthyl-8l8-dicarb0xylic vat dyestufi's are obtained by treating with acid and its substitution products of the gen- 5 acid condensing agents at moderate condieral' formula:

(wherein the Xs stand for hydrogen atoms, jecting to the action of acid condensing of which ,one or more may lie replaced by a agents the condensation products this ob- 15 monovalentsubstituent, the Ys stand for tained. 10 hydrogen-atoms, which may be replaced by The new intermediate products formed in halogens), then heating wlth alkaline conthe difi'erent phases of the process have probdensing agents the benzobenzanthrone-carably the following general formulae: boxylic acids thus obtained and finally sub- (wherein the X7s stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, the Ys stand for hydrogen atoms, which may be replaced by halogens) an Y (wherein the Xs stand for hydrogen atoms,

of which one or more may be replaced by a monovalent substituent; the Ys stand for hydrogen atoms, which may be replaced by halogens) while the final products have probably the following formula which corresponds to the violanthron type:

. Y v (wherein the Xs stand for hydrogen atoms, of which one or more may be replaced bya monovalent substituent; theyYs stand for hydrogen atoms, which may be replaced by halogens).

The vat dyestuffs obtained by this process are insoluble in water, alkalies and 1n the usual organic solvents, soluble in concentrated sulfuric acid with a yellow to olive color, forming violet colored vats from" which cotton is dyed blue to gray shades, fast to washing, chlorine and light.

The 1.1 dinaphthyl-8.8' -dicarboxylic acid as the starting material is obtainable for instance by saponifying its. diethylic ester, which Kalb (see Berichtb der deutschen Chemischen Gesellschaft, vol. 47, page 17 24) has prepared by treating thoic. esters with copper powder.

The nuclear substitution products of the 1.1'-dinaphthyl-8.8-dicarboxylic acid may be obtained either by saponifying the corresponding esters, which are described in the German Patent No. 280787, for instance b heating them with alcoholic hydrochloric acid for alcoholic alkalies, or by substituting directly the 1.1 -dinaphthyl-8.'8 -dicarboxylic acid itself. It yields, when brominated in glacial acetic acid, a monobromoproduct, crystallizing from trichlorobenzene in yellow crystals and melting above 300 0., when treated with an excessof bromine in the cold with alkaline hydrosulfite blackish 1-chloro-8-naph- I an orange'colored dibromocompound, melting further illustrate our invention the following examples are given; we WIS 1t however understood that we are not limited to the particular examples given nor to the specific conditions mentioned. The arts are by weight and all temperatures in centigrades.

Ewample 1.

10 boxylic acid areboiled under reflux while stirring with 200 parts of glacial acetic acid and 20 parts of anhydrous zinc chloride, until the starting material is dissolved. After d1- luting the solution with water the benzo;

benzanthrone-carboxylic acid, thus formed.

separates. 4

The newcompound crystallizes from a parts of .the 1-.1'-dinaphthyl-8.8'-dicar{ mixture of glacial acetic acid and alcohol-in k yellow prisms, meltin at 27 8, andis easily soluble in alkalies wit a yellow color and in cold concentrated sufuric with a brown 7 ish red color.

' Ewample F3.

Into a suspension of 10 parts of the 1.1'-dinaphthyl-8.8'-dicarboxylic acid in 48 parts of sulfuric acid of 48 p. c. strength 230 parts of sulfuric acid of 66 B. are allowed to benzobenzanthrone-carboxylic jecting derivatives and substitution products of the 1.1-dinaphthyl-8.8 dicarboxylic acid to the same process.-

For instance by startin froma monobromo 1.1 dinaphthyl 8.8 -dicarboxylic acid the corresponding monobromobenzobenzanthrone-carboxylic acid is obtained, cryst-alliz- 1 ing from trichlorobenzene in yellowish orange needles, melting at 288290. soluble in sulfuric acid of 80 p. c. strength with a red color.

The dibromodinaphthyldicarboxylic acid yields, when treated in an analogous man ner, a dibromobenzobenzanthrone-carboxylic acid, crystallizing orange colored crystals, melting above 300 and diificultly soluble in cold sulfuric acid of 80 p. c. strength'with an olive color.

T h e monochlorodinaphthyldicarboxylic acid forms a monochlorobenzobenzanthronecarboxylic acid, melting at 268-269, when crystallized from monochlorobenzene, corre sponding in its properties to the monobromocompound.

Ewample 3.

At about 95 10 parts of the benzobenzanthrone-carboxylic acid, described in Example 1, are introduced into a mixture of 100 parts of caustic potash and 60 parts of alcohol. The temperature of the mass is maintained for some hours. Then the mass is dissolved in water and the solution is treated with air or another suitable oxidizing agent in order to oxidize the formed leucocompound of the condensation product. From the blue solution, thus obtained, the condensation product is isolated in the usual manner either by precipitating with acids or by adding common salt to the solution.

when warmed. With an alkaline hydrosulfite sol'ution'ablue solution is obtained, havinfia red fluorescence.

y using derlvatives or substitution products of the benzobenzanthrone-carboxylicf cotton dyed the'same Shade, turning to a greyish green blue ofan excellent fastness,

acid analogous condensation products 'of similar properties are obtained.

Ewample 4.

10 parts of the ben zobenzanthrone-can boxylic acid and 20 parts of pulverizedcaustic thus,

It is from trichlorobenzene in warmed diluted alkaline ably the formula The new carboxylic acid is when dry a blue powder, easily soluble potash are boiled for about 6 hours under reflux with 120 parts of pyridine, while stirring. After diluting the mass with water the pyridine is expelled by steam and the alkaline solution islworked up, as described in Example 3. Y The compound, thus obtained, is identical with the product prepared according to Example 3. 7

By using other solvents or 'diluents such-as aniline, dimet-hylaniline, naphthalene, the same result is obtained, Also the caustic potash may be replaced by other alkalinecondensing agents, dium-amide, sodium alcoholate.

Example 5. 10 parts of the product, describedin Examsuch as aniline-sodium, so-

ple 3, are introduced in 200 parts of sulfuric acid of 66 B. The solution is stirred at an ordinary temperature, until a sample, precipitated with water, is no longer soluble in alkalies. The reactlon may be accelerated by warming the solution.

is filtered, washed and dried. Impurities may be removed by carefully treating it with a sulfite. The purified dyestufi", having probis when dry a bluish black powder, insoluble in the usual organic solvents, soluble in concentrated sulfuric acid to a yellowish olive solution. It formswith an alkaline solution of hydrosulfite a black-violet vat, from'which when the dyed goods are allowed to drain or product, described in Exarn'ple-3, its derivatives or substitution products, analogous dyestuffs of similar properties are obtained. For instance by starting from a bromobenzoben The mass is then .di- 'luted with water and the separated dyestufl solution of hydro-' (wherein the zanthron-carboxylic acid a dyestuff is obtained dyeing cotton from the vat bluish shades, by starting froma chlorobenzobenzanthroncarboxylic acid a grey dyeing dyestuif is obtainable in the same way, i

We claim:

1. As new products vat dyestulfs, having probably the general formula I stuffs are substantially identical with the dyestuffs obtainable by treating 1.1 -dinaphthyl- 8.8-dicarboxylic acids of the general mula:

' boxylic acids of for- (wherein the Xs stand for hydrogen. atoms, of which one or more may be replaced by a monovalent substituent, the TS stand for hydrogen atoms, which may be replaced by halogens) with acid condensing agents at moderate conditions by treating then the products 7 of condensation with alkaline condensing agents and by subjecting finally to the action of acidcondensing agents the products of condensation thus obtained.

2. A new'process of making new vat dyestufis by treating 1.1.-dinaphthyl-8.8-dicarthe general formula:

(wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, the Ys stand for 'hydrogen atoms, which may be replaced by halogens) with "acid condensing agents at moderate conditions, by treating tlien the products agents and by subjecting finally to the action of acid condensing agents the products 3. A new process of making new vat dye* stuffs by "treating benzo-benzanthrone-carjof condensation with alkaline condensing of condensatlon thus obtained.

boxylic acids of the general formula:

aria;

(wherein the Xs' stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, the Ys stand for hydrogen atoms, which may be replaced byhalogens) with alkaline condensing agents and by 12: subjecting to the action of acid condensingagent; the products of condensation thus obtaine 1 king new vat dyesoluble carboxylic acids, having probably the gen CODE (wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a 3 monovalent substituent, the ,Ys stand for hydrogen atoms, which may be replaced by halogens) to the action of acid condensing agents. a

with an acid condensing agent at moderate conditions, by treating then the product of condensation thus obtained With an alka- 80 line condensing agent and in subjecting which dyestufl h 'tion and yielding with tained.

,817 5 I 5. As a new product the vat dyestufi', having probably the formula: 3/! 5I\ 4 y 1' s' as a great aifinity to the vegetable fibre, being when dry a bluish black powder, insoluble in water, alkalies and the usual organic solvents, soluble in concentrated sulfuric acid to ayellowish olive soluan alkaline hydrosulfite solutlon a black-violet vat, from which cotton is dyed the same shade turning to green-blue; when the goods are allowed to drain or soaped, which dyestuif is substantially identical with the dyestufl obtainable by treating the 1.1-dinaphthyl-8.8-dicarboxylic acid of the formula:

of an acid condensing finally to the action condensation thus obagent the product of 6. A new process of producing a new vat dyestufi by treating the 1.1'-d inaphthyl-8.8- dicarboxylic acid of the formula:

with an acid condensing agent at moderate conditions by treating then the productof condensation with an alkaline condensing. agent and in subjecting finally to the action I of an acid condensing agent the product of condensation thus obtained.

7 A new process of boxylic acid of the probable-formula:

GOOH

with an alkaline condensing agent and by sub,-

5 jecting to the action of an acid condensing making a new vat dyestuff bytreating a benzo-benzanthrone-caragent the product of tained.

8. A new process of stufi by subjecting acarboxylic acid of the probable formula: a a

condensation thus obmaking a new vat dyeto the action of an acid condensing agent.

tures.

phenom WERNER In testimony-whereof, we afiix our signa- ZERWECK.

KALISCHER. 

